Pressurized decorative spray-package



Unite 2,982,743 Q'PRESSURIZED DECORATIVE SPRAY-PACKAGE :Charles-HaClapp, Jr.,'Danville,-and TheodoreA. Thonet, Westville, --Ill., assignorsto Continental -Filling CorkporationfDanville, 11]., a corporation of Illinois No Drawing. FiledFb.-1,'-1 960, Sen-No. 5,590

4 Claims. c1. 260-43 'Ihis invention relates to a pressurized package to. be used for the production of decorative sprays *su'chas-the --'so:calleda1tificial snows which have become 'popular 1 ,efiubracarbons mhese r ennamgenguaio qj arim.wveiglit hydrocaibons"' inEwhich ahleastRo Or-artificial snow, etc., etc.

liq'uid contents thr'ough the dip tube and out ofj'the nozzle Stat s 31 c6 2,982,743 Patented May 2,1061

halogens is fluorine, and usuallyat least one is chlorine. They have the formula C Cl FXY wherein n is a whole number from 1 to 3, X is chlorine or fluorine, and Y is chlorine, fluorine, bromine, iodine -or-hydrogen. Examples of these are trichloromonofluoromethane, dichlorodifluoromethane, chlorotrifiuoromethane, dichloromonofluorqmethane, difluoromonochloromethane, t'richlorotrifluoroethane, dichlorotetrafiuoroethane, monochloropentafluoroethane, and chlorodifluoromethyl methane, which haveboiling points ranging from about 30 C. to50'C. Y 1 r These'are sold by duPont 'underthe trademark "Ereon "and by other manufacturers under various other trademarks.

These propellants may be replaced ,in part ,by other propellants, tor-example, low boiling hydrocarbons, *such as isobutane, normal butane,-propane, etc. Such-h-ydro- :carbon propellants cou'ldbe used by-themselves except "dustr y. Ar'nong the most commonare'the*so-called'Fbeer can containers of-about 6-16 ouncecapacityin which 'a -=vafiety "of pressurized -self=spraying formulations are Lsld including insecticides, deodorants', waxes, "simulated {The container is equipped with a quick acting valve of th'e type which will'caus e the formulationtoibeejected asa wet-spray'when the valve is actuated. 'Fbeformu- -1at'lbn 'lS broken up into small droplets which are deposited on'rthe target. This is in contrast with the types of valves producing a space-spray which comprises amist 'or fog;'or' the typeproducing a foam; or stillianother. type 'produc'ing 'a jet stream. There are a nu'rnber of comm ei'cially available valves suitable for use in this' i nfirentiom andtheyneed-not bedes crib'e'd in detail. llilsually th'e'y are equipped with-adip tube which extends to the bottom, or near the "bottom of the container. j Thepres- -sur-bf the propellant vapor in the container; or'cesflthe,

of the valve from which it emerges as a wet spray .and is deposited on the target being -deco-ratedL -The container is usually filled to about 85-95 70 of its wolume'with a liquid form'ulationof this invention, al-

though this may vary considerably one way or theother. 'Methods of filling such containers are well known and nejed. not be described in detail.

" lhe' fiormulation of this, invention consists esseniially that they are flammable and hence may present ;a --fir e hazard; Consequently, the proportion; of such hydrocarbon propellant is usually not morethan-about 4 0% of the total formulation.

The fatty acid should be solid atroom'temperature (e.g. about 70-85 F.) and may-suitably comprise -1 -2-;-l8 carbon atoms. Higher molecular weight acids may be used provided they are sufliciently soluble. Suitable acids are-stearic, palmitic, myristic, ricinoleic, etc., orrni-xtures thereof. Many-commercial acids are mixtures in which one or another acid predominates, and such mixed acids .are satisfactory provided they produce no odor problem. The preferred acids :are' saturated, since unsaturatedlacids may become rancid. From price ;cons iderations,- aswel;l

'as performancejstearicr acid or n-iixturesdn'whichitpfethat it will evaporate readily as soon as the formulation is -sprayed; fatty acid should 'be readily soluble in th'e solvent-"at'relatively low temperatures, s'ay -60- F to which the packages may sometimes be subjected. :It

should also be misciblewiththepropellantf Thesolvent',

i or at least- -the-combination of solvent 'and propellant should also "be capable of dissolving the resin and -keepchloroform, chloroform and other -relativel-y lowboiliiig' chlorinated hydrocarbons; Trichlorofluoromethane in *ptheri non-propell-ant 'chlorofluoro hydrocarbons may be used-provided the acid is {sufliciently-"seluble "therein.

Mixtures of solvents njray be used. Anyforganic-solveiit {which is readily volatile a't {room temperature may "be employed. From-a practical standpoint; solvents pro 'senting 'o'dor or firehaiard prob1eins,-orwl1ich are highly toxic should not be..used,-nor should those having pressures so low that they do not evaperatereadily.

' The resinrcomponent is ahigh molecular'weight-polyalkylene oxide su'ch polyethylene-oxide, -polypi opylene ark- '1 a-propellant which is gaseous ,under normaltempefature and pressure "conditions; (2). anoifmally, solid, free, fatty acid having forexample 1'2 -18 carbon atoms -pe'r molecule; (3)a-solvent'for the fatty acid; and (4)1a small amount of a polyalkylene oxide havinga molecular weight in excessof200,000; and preferably' of about 500,000 or more, which serves to cause'the'fattya'cid -to assume the desired flake .form. when propelled against 3 aihei tar getfi a The propellants suitably comprise'the normal-lyg gaseous oxide, polybutylene oxide and the like. lit-should; have -=a?' molecular for the various components based on the total com- 1 Based on total composition. Amount used depends on molecular weight of the resin and the proportion of fatty acid employed.

The following comprise specific examples of suitable compositions. I A base composition was made up as follows:

. 7 Percent by weight 'Stearic acid (double pressed) 16 Methylene chloride e 44 .Difluorodichloromethane 40 These components formed into a solution and charged form a suitable decorative spray-coating, but rather resembles sprayed talcum powder. I

' When a suitable polyethylene oxide is dissolved in the formulation the dispensed spray is deposited in flake-like particles on the target forming an excellent simulated snow decoration.

to a suitable valved container cannot be dispensed to 1 The following table shows suitable proportions of polyethylene oxide polymers of varying molecular weight. 3 p p Proportions Formula Tradename 1 Approximate Added To I M01. Wt. BaseFormula,

- p.p.n1.

'1" Polyox coagulant.-. 5,000,000 150 (100-300) 2 Polyox WSR L---" 3, 500, 000 300 (200-600) '3" I 2,000,000 950-1, 250 4 Polyox WSR 205 500, 000 1, 250-1, 550 6 Polyox WSR 200, 000 35, 000 (3. 5%)

Tr ad emarkOarbide & Carbon Chemical 00.

than about 0.25% by weight of the total compositiomand '1' "usually below about 0.15to about 0.2%. For this reason the lower molecular weight polyalkylene oxidesiare not equivalent to thoseof about 500,000 or more.

The polyalkylene *oxides have unique characteristics; Six to eight times as much of a polyvinyl acetateresin of 2,000,000 molecular weight: is required as for-a polyethylene oxide of corresponding molecular weight. .Otherhigh molecular weight'resins (e.g. 1.5-2.5 million) such as, polyacrylates and methacrylates must be used in -large amounts, or mustbe used together with'1-4% of 00 another plastic-resin of considerably lowermolecular ,weight ('e.g. polyvinylacetate, 90,000 m.w.);,? Thus,'the

advantages of the polyalkylene oxides used, in this invention are readily app rent;

not onlyon themolecular weight, but,also-;on the proportion of acid used in the ,base formulation. .1 Thus,

the base formula containing" 16% stearic; :-acid, about 100-250 p.p.m: maybe employed. If morefthan about.

300 ppm. of this Polyoxis usedgthespray resembles v coconut shreds orspaghetti, rings. .If omitted entirely,

theacid is dispensed as apowderr.

If the acid proportion islreduced, for example,..to

1, The proportionof polyalkylene oxide used depends:

when' ,'the Polyoxcoagulant of Formula lfis used with a polyethylene oxide If the acid content is increased, the Polyox can be increased proportionately.

There is, however, a limit to the proportion of acid which can be employed, this being based upon the solubility of the acid in the solvent-propellant at both the dispensing temperature and a temperature somewhat lower, e.g. 40-60 F., since the package may sometimes be stored at such lower temperatures and separation of the solids is undesirable.

The proportions of solvent and propellant may vary. Since the propellant is usually the most expensive component of the composition, it is desirable to keep it as low 'as possible and still obtain the desired dispensing efiect. This depends upon the vapor pressure of the particular propellant andits partial pressure in the mixture. This in turn is affected by the vapor pressure efiect of thesolvent. The absolute package pressure can be governed to some extent by the proportions of solvent and propellant, or by the use of more than one propellant and/orsolvent. I

. The-amount of a given solvent may also be limited by characteristics of the package parts, particularly valve seal rubbers. This is, of course, a matter of practical consideration, not directly related to this invention. In

the base formula given above, a substantial increase in methylene chloride proportion would result in somerubber deterioration. As more resistant rubbers become available this factor becomes less critical. 7

g The polyalkylene oxidesmay be polymers of ethylene oxide, propylene, oxide, or butylene oxide, etc., polyethylene oxide being preferred.

The formulations of this invention have advantages over these heretofore used. They are more readily cleaned from draperies, furniture, windows, etc. than earlier formulations because the solids deposited consist almost entirely of the organic acid which is readily .washed off with water and a detergent such as soap, am-

monia, etc. Moreover, the polyalkylene oxides are largely water soluble, and are present in such low proportions as to have little effect on cleaning even if they were not. of plastics, many of which-were not water soluble, were difficult to remove from the target. For example, earlier formulations contained resin to'acid in ratios of 1:4 to 1:1 parts or higher. In the present invention the ratio of polyalkylene oxide to acid is in the range of about 1:500-1600 parts by weight. i

The inclusion of small amounts of the. polyalkylene oxides in the compositions of the character dealt with here and containing other plastic resins as well'as; solid fatty acids), permits substantial reduction in the amount of such other resins and provides increased performance characteristics to the resultant compositions. t

. The examples givenare'for purposes of illustration an should not be construed asilimiting the invention unduly.

. We claim as our invention: i

1. In a pressurized self-spraying decorative spray coniposition comprising a normally solid free fatty acid such as those containing 12-18 carbon atoms per molecule,'-;a solvent for said acid, and a liquefiednormally gaseous propellant, the improvement which comprises incorporating in the composition about to'about 250,0 p.p.m. .of a polyalkylene oxide having fromtwo to-four carbon atoms in the monomer unit, and a moleculanweight above about 200,000, based on the total formulation,

J l. Ina pressurized self-spraying decorative Spray cOmposition comprising a normally solidfree fatty acid such ,as .those containing 12-18 carbon atoms "permolecule,

-asolventtorfs'aidacid, and aliquefiednormally gaseous propellanuf the, improvementwhich comprises incorpO1iaZting in'the composition about 100 to about 2500 ppm. of

tom 00 9 0. I

. 3. ;'I'h'e,composition of claim 2.;wherein the, polyethylene $17 09? m ssed Rama siz sqss qtrt pt ne s w te19r ds,,.h s. mol c r .iweighr of amour 509,000; to about Earlier compositions containing higher percentages having a molecular weightyabove 5,000,000 and the weight ratio of polymer to amid is in the range of about 12500-1600.

4. A pressurized self-spraying decorative spray composition comprising about 5% to of a normally solid free fatty acid having from about 12 to about 18 carbon atoms per molecule, about to about solvent for said acid, about to about 250 p.p.m. of polyethylene oxide, having a molecular weight above 500,000, the remainder consisting essentially of a liquified normal- 1y gaseous propellant.

References Cited in the file of this patent UNITED STATES PATENTS 

1. IN A PRESSURIZED SELF-SPRAYING DECORATIVE SPRAY COMPOSITION COMPRISING A NORMALLY SOLID FREE FATTY ACID SUCH AS THOSE CONTAINING 12-18 CARBON ATOMS PER MOLECULE, A SOLVENT FOR SAID ACID, AND A LIQUEFIED NORMALLY GASEOUS PROPELLANT, THE IMPROVEMENT WHICH COMPRISES INCORPORATING IN THE COMPOSITION ABOUT 100 TO ABOUT 2500 P.P.M. OF A POLYALKYLENE OXIDE HAVING FROM TWO TO FOUR CARBON ATOMS IN THE MONOMER UNIT, AND A MOLECULE WEIGHT ABOVE ABOUT 200,000 BASED ON THE TOTAL FORMULATION. 